|Publication number||US6843938 B2|
|Application number||US 10/388,140|
|Publication date||18 Jan 2005|
|Filing date||13 Mar 2003|
|Priority date||13 Mar 2002|
|Also published as||US20030209694, WO2003078543A1|
|Publication number||10388140, 388140, US 6843938 B2, US 6843938B2, US-B2-6843938, US6843938 B2, US6843938B2|
|Inventors||Paul H. Holloway, Mostafa Abboudi|
|Original Assignee||University Of Florida Research Foundation, Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (11), Non-Patent Citations (2), Classifications (15), Legal Events (7)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This application claims the benefit of U.S. Provisional application No. 60/364,838, filed Mar. 13, 2002.
This invention was made with government support under a grant awarded from DARPA to Georgia Tech under grant number MDA972-93-1-0030 with a subcontract to the University of Florida and administered at the University of Florida under grant number 450947012. The government has certain rights in the invention.
The present invention pertains to advantageous new low temperature processes for synthesizing rare-earth oxysulfide light-emitting phosphors.
Oxysulfide phosphors, which are used in all of the display technologies, are desirable commercial products because of their high luminance efficiency. For example, red, green, and blue emitting phosphors (three different phosphors) are used in every television, computer monitor, and cathode ray tube produced. They are used in electron beams and X-ray digitized image displays. Phosphors are also used in the lighting industry, for example, in fluorescent light bulbs.
Current oxysulfide phosphor synthesis methods produce phosphors with sufficient luminosity, but these processes have significant disadvantages in terms of operating costs and processing time. For example, current methods require process temperatures in excess of 500° C. In one method, process temperatures as high as 1350° C. are reached in production of oxysulfide phosphors. Operating and equipment costs associated with reaching and maintaining temperatures of this magnitude create a need for lower temperature methods of preparation.
In addition, some methods require inert gases such as nitrogen for the reaction environment. The extra equipment for maintenance of the inert atmosphere in addition to the operating expense of buying a specialty gas creates a need for a process utilizing cheaper accessible reactants.
Also, reaction times are frequently an hour or more. Combined with the multiple steps required to prepare, react, and purify the oxysulfide phosphor, the total processing time is often hours. A shorter reaction and processing time is desirable because product may be made more frequently or on short demand time.
Therefore, it is desirable to find a method to produce rare-earth oxysulfide phosphors without the disadvantages of the known methods, thus reducing the operating costs. Because both the display and lighting markets, which deal with consumer items, are very cost competitive, any process that reduces cost will have a huge potential impact.
The present invention provides new and useful methods for preparing rare-earth oxysulfide phosphors. Rare-earth oxysulfide phosphors, materials that emit electromagnetic radiation when excited, are useful in many commercial areas including electronics containing cathode ray tubes and medical devices that utilize X-rays.
Advantageously, in accordance with the methods of the subject invention, rare-earth oxysulfide phosphors can be prepared with lower reaction temperatures and fewer processing steps than methods currently in use.
In a preferred embodiment, the process of the subject invention involves blending two different rare-earth nitrate salts and a sulfidizing agent. After being thoroughly combined, the mixture can be dried to prevent any hydration of the nitrate salts before the combustion step. Then, the mixture is heated in a furnace to the necessary temperature, preferably around 200° C. to 300° C., until the rare-earth oxysulfide phosphor is produced.
If particle sized phosphors are desired, the agglomerated phosphor nodules produced by the process of the subject invention may be ground without compromising the cathodoluminescent efficiency of the phosphor. In addition, an annealing step to increase the photoluminescence of the phosphor may be added. The annealing step can follow the grinding step.
In a specific example, the subject invention provides new and unique methods for preparing oxysulfide phosphors with the general formula Ln2O2S (where Ln is scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium). The phosphors produced according to the subject invention comprise a small amount, typically less than about 5%, of a second Lanthanide Group element that is incorporated within the Ln2O2S matrix.
The present invention, operating with a simple procedure at reduced costs in terms of energy, time, and starting materials, results in significant cost savings while producing commercial quality rare-earth oxysulfide phosphors. This invention allows mass production of oxysulfide phosphors; the methods of the subject invention have the following very desirable characteristics:
the short time of reaction and low temperature results in very low energy costs;
the process is simple in comparison with existing processes, and the reaction can be done in the presence of reasonable quantities of oxygen;
many, or all, of the reagents are commercially available;
compounds can be prepared in a few minutes; and
the compounds obtained according to the subject invention have a brightness equal to the present commercial products and, in some cases, higher intensity peaks for green or red emission.
The present invention provides unique and advantageous processes for manufacturing rare-earth oxysulfide phosphors. Advantageously, the methods or the subject invention for synthesizing rare-earth oxysulfide phosphors reduces the number of steps of production, decreases the energy costs by requiring lower temperatures, and uses commercially available components.
In a preferred embodiment, the oxysulfide phosphous produced according to the subject invention have the general formal Ln1 2-xLn2 xO2S, where Ln is a member of the Lanthanide group of elements. The term “Lanthanide” is used herein to denote elements with an atomic number from 57 to 71 (i.e. from lanthanum to lutetium). In a preferred embodiment, the value of x is between about 0.0005 and 0.5. More preferably x is between about 0.001 and 0.1.
A phosphor is a material, which, when excited by electrons, photons, or electric fields, emits electromagnetic radiation. In the present case, the light can be emitted in the visible or infrared regions. These phosphors can be in the form of a solid solution having a matrix of the rare earth oxysulfide compound detailed above but doped with a small amount of an activator dispersed throughout the matrix. The activator is typically also a rare-earth element.
Advantageously, the luminescent phosphors produced according to the subject invention maybe used in a number of applications. Examples of applications of two of these types of phosphors include: production of the red phosphor used in television screens: Y2O2S:Eu and production for an intensifying screen for X-rays: Gd2O2S:Tb.
In a preferred embodiment, the rare-earth oxysulfide phosphors are obtained in accordance with the present invention by heating a blend of two different rare-earth nitrate salts and a sulfidizing agent. More specifically, a rare-earth oxysulfide phosphor can be obtained by blending a rare-earth element in its nitrate salt form with a smaller quantity of a different rare-earth nitrate salt. Using techniques known in the art, the two salts are broken into smaller nodules or particles by grinding. An organic sulfidizing agent is blended with the salt mixture followed by additional grinding. Preferably, dithiooxamide is added as an organic sulfidizing agent.
To fabricate the phosphors in accordance with the subject invention, the nitrate and sulfidizing agent blend is heated to temperatures less than 1000° C. Preferably the blend is heated to a temperature between about 200° C. and about 300° C. Most preferably, the blend is heated to around 230° C.
In one embodiment, to inhibit the hydration of either of the rare-earth nitrate salts, the salt and sulfidizing agent blend is dried before combustion occurs. One embodiment utilizes a desiccator as a preferred technique for drying. The drying time will vary depending upon which rare-earth nitrate salts are used, and can be readily determined by a person skilled in the art. As would be appreciated by the skilled artisan, for certain nitrate salts no drying time would be needed but, for other salts, up to around one week of drying may be employed.
The phosphors produced according to the subject invention can be further processed to optimize the physical properties of the phosphors to meet specific market needs. In one embodiment, the phosphor can be ground using techniques known in the art to fracture the phosphors into individual particles without decreasing cathodoluminescence. In another embodiment, the individual particles can undergo an annealing step after the post-combustion grind to increase the photoluminescence of the particles.
Depending on the host lattice and the activator(s), the conditions of the subject method can vary. With the benefit of the teachings provided herein, optimum conditions can be established, by a person skilled in the art, for each combination of rare earth salts. Factors that can be optimized include:
the ratio of sulfidizing agent to nitrate (this ratio varies because of the energy and temperature obtained varies for each reaction); and
drying time (varies from no time up to a week or more)—this parameter varies because of the different tendencies for hydration of the nitrate salts of different rare-earth elements.
Following are examples that illustrate procedures for practicing the invention. These examples should not be construed as limiting.
To prepare an oxysulfide phosphor with the formula La1.936Eu0.064O2S, which corresponds to doping with 3.2% of europium, the starting compounds shown in Table 1 can be used.
In the first step, the nitrate salts of the rare earths can be put in a mortar and ground, producing a good homogeneity of the nitrates. Then, an organic sulfidizing agent, in this case the dithiooxamide (C2S2N2H4), is added to the mixture of nitrates. The mixture is again thoroughly ground (approximately 15 minutes). This mixture is put in a combustion boat in a desiccator for 24 hours. When the mixture is heated in a furnace at 230° C. in air, a highly energetic reaction takes place in only a few seconds.
The very porous oxysulfide of lanthanum obtained is shown by the scanning electron microscopy (SEM) photomicrograph in FIG. 1. The morphology of this powder (
The X-ray diffraction (XRD) spectrum shows only La2O2S, without a presence of any secondary phases (FIG. 2). Cathodoluminescence emission has been studied at a voltage of 2 keV, and
For the preparation of a phosphor with the formula La1.936Tm0.064O2S, which corresponds to doping with 3.2% thulium, the starting compounds shown in Table 2 can be used.
The method of preparation is exactly the same as in Example 1.
For the preparation of a phosphor with the formula Gd1.996Tb0.004O2S, which corresponds to doping with 0.2% terbium, the starting compounds shown in Table 3 can be used.
The same process is used as described above, but in this case, the time of drying in the desiccator is increased (to one week) because of the higher tendency of the gadolinium nitrate to hydrate. With longer drying times, a pure oxysulfide of gadolinium is obtained. As characterized by XRD (FIG. 5), only one crystalline phase was formed and it is the expected oxysulfide of gadolinium.
The powder morphology as imaged in the SEM again shows grain sizes less than one micrometer (FIG. 6).
The cathodoluminescent spectrum from excitation with a primary electron bean of 2 keV is shown in FIG. 7. It is that expected from Tb doped gadolinium oxysulfide, i.e., a very bright green emission.
For the preparation of a phosphor with the formula Y1.996Tb0.004O2S, which corresponds to doping by 0.2% terbium, the same method is used. The starting compounds are in Table 4.
In this case the molar ratio of organic sulfidizing agent to rare-earth nitrate is equal to 1.8 in order to reduce the organic residue. The XRD pattern from these powders is shown in
The SEM photomicrograph in
Finally, the 2 keV cathodoluminescent spectrum shown in
Powders of Ln2O2S (in this case, Ln=La, Gd, Y) containing luminescent activation centers of either Eu+3, Tb+3, or Tm+3 have been prepared by combustion reactions using metal nitrates and dithiooxoamide ((CSNH2)2). Their cathodoluminescent properties have been measured versus activator type and concentration, current density, and beam energy. Measurements of the relative peak intensity for 5D2→7F4 (534 nm) and 5D1→7F3 (589 nm) to 5D0→7F2 (627 nm) in La2O2S:Eu+3 phosphor have shown that at high activator concentration, emissions from high energy levels, (5D2 and 5D1), are more suppressed than from the low energy level, (5D0). The 5D2→5D0 and 5D1/5D0 ratios have also been decreased when current density and beam energy were increased. In addition, matrix effects can lead to quenching of Eu emission from 5D2, 5D1, and 5D0 levels and suppression of high energy level emission from Tb oxysulfides.
The emission intensity from the 5D2→7F4 (534 nm) and 5D1→7F3 (589 nm) to 5D0→7F2 (627 nm) luminescent transitions in Eu+3 doped Ln2O2S (Ln=La, Gd, Y) powder phosphors prepared by combustion reaction have been studied. It has been shown that emissions from high energy levels (5D2 and 5D) are suppressed relative to those from low energy level (5D0) at higher current density (e.g. 30 vs, 200 uA/cm2) and beam energy (e.g. 2 vs. 5 keV). It has also been shown that the decay of the emitted intensity during electron-beam radiation is greater from 5D2→7F4 (537 nm) and 5D1→7F3 (586 nm) transition vs. 5D0→7F2 (624 nm) at a current density of 200 uA/cm2. However, no decay was observed for these transitions at a current density of 30 uA/cm2. These results can be interpreted in terms of perturbations to the energy transfer process (e.g. electrostatic dipole and magnetic dipole interactions) by internal electric fields those are induced by charging, and due to thermal quenching caused by electron-beam heating. In both cases, quenching of emission from higher excited states can be expected at higher current density and beam energy.
It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3878119||26 Dec 1972||15 Apr 1975||Gen Electric||Preparation of rare-earth oxysulfide phosphors|
|US3980887||11 Apr 1975||14 Sep 1976||U.S. Radium Corporation||Silicon sensitized rare earth oxysulfide phosphors|
|US4473518 *||16 Jul 1982||25 Sep 1984||Mitsubishi Chemical Industries Ltd.||Process for preparing a phosphor|
|US4510414 *||23 Jul 1982||9 Apr 1985||Fuji Photo Film Co., Ltd.||Electron excited fluorescent display device including screen with rare earth phosphor exhibiting sublinear current density-emission luminance characteristics|
|US5217647||1 Mar 1991||8 Jun 1993||Kasei Optonix, Ltd.||Method for preparing rare earth oxysulfide phosphor|
|US5879587||24 Sep 1997||9 Mar 1999||Osram Sylvania Inc.||Terbium-activated rare earth oxysulfide phosphor with enhanced green:blue emission ratio|
|US6103296 *||22 Apr 1998||15 Aug 2000||Osram Sylvania Inc.||Method for improving the screen brightness of gadolinium oxysulfide x-ray phosphors|
|USRE29662 *||4 Apr 1977||6 Jun 1978||Rca Corporation||Rare earth activated lanthanum and lutetium oxy-chalcogenide phosphors|
|EP0471091A1||1 Mar 1991||19 Feb 1992||Kasei Optonix, Ltd.||Process for producing rare earth oxysulfide phosphor|
|EP0908503A1||20 Jun 1997||14 Apr 1999||Kasei Optonix, Ltd.||Rare earth sulfate phosphor and x-ray detector using the same|
|EP1236784A1||1 Dec 2000||4 Sep 2002||Kasei Optonix, Ltd.||Method for producing phosphor|
|1||Chen, Jing-Ran, Maria T. Dunlay, Richard N. Zare (Mar. 15, 2000) "Macroporous Photopolymer Frits for Capillary Electochromatography" Anal. Chem. 72(6):1224-1227.|
|2||Valaskovic, Gary A. et al. (Oct. 15, 1995) "Attomole-Sensitivity Electrospray Source for Large-Molecule Mass Spectrometry" Anal. Chem. 67(20):3802-3805.|
|International Classification||C01F17/00, C09K11/77, C09K11/84|
|Cooperative Classification||C01F17/0093, C09K11/7789, C01P2002/84, C01P2004/62, C01P2002/72, C01P2002/54, C09K11/7771, C01P2004/03|
|European Classification||C01F17/00N2, C09K11/77S2H4, C09K11/77T2H4|
|10 Jun 2003||AS||Assignment|
Owner name: FLORIDA, UNIVERSITY OF, FLORIDA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HOLLOWAY, PAUL H.;ABBOUDI, MOSTAFA;REEL/FRAME:014151/0484
Effective date: 20030331
|26 Apr 2004||AS||Assignment|
Owner name: UNIVERSITY OF FLORIDA RESEARCH FOUNDATION, INC., F
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:UNIVERSITY OF FLORIDA;REEL/FRAME:014563/0675
Effective date: 20031215
|31 May 2005||CC||Certificate of correction|
|3 Jul 2008||FPAY||Fee payment|
Year of fee payment: 4
|3 Sep 2012||REMI||Maintenance fee reminder mailed|
|18 Jan 2013||LAPS||Lapse for failure to pay maintenance fees|
|12 Mar 2013||FP||Expired due to failure to pay maintenance fee|
Effective date: 20130118